US3268393A - Method of killing insects with phosphorodithioites and phosphorodithioates - Google Patents
Method of killing insects with phosphorodithioites and phosphorodithioates Download PDFInfo
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- US3268393A US3268393A US456474A US45647465A US3268393A US 3268393 A US3268393 A US 3268393A US 456474 A US456474 A US 456474A US 45647465 A US45647465 A US 45647465A US 3268393 A US3268393 A US 3268393A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
Definitions
- This invention relates to the control of agricultural pests. More particularly it relates to the control of insects, mites, and symphylans with S,S-dipropyl O-methyl phosphoridithioite or a compound of the formula wherein R' is selected from the group consisting of methyl and ethyl, R is a member of the group consisting of propyl and butyl when R is methyl, and R is propyl when R is ethyl.
- the compounds of this invention may be prepared by reacting substantially two moles of the appropriate alkyl rnercaptan with essentially one mole of phosphorus trichloride, and reacting the resulting dialkyl phosphorochloridithioite with one mole of methyl or ethyl alcohol.
- the S,S-dialkyl O-methyl or O-ethyl phosphorodithioite thus formed may be converted to the corresponding dithioate by reacting it with an oxidant such as hydrogen peroxide.
- organophosphorus compounds of the invention have been found useful for the control or insects, mites, and symphylans at concentrations of from 0.005 to 1% by weight of the total formulation. Because of the low rates required for effective control, it would be impracticable to apply the compounds as such. It is desirable, therefore, to apply them in the form of liquid sprays, or as formulations containing solid vehicles or extenders, in either case the formulation comprising a minor amount of the active ingredient.
- the compounds may be mixed with a finely divided solid carrier as an aid in uniform distribution.
- acceptable solid carriers are those which are non-hygroscopic (to prevent caking) and inert (to eliminate undesirable adverse effects upon the formulation itself and upon the environment to be treated).
- Some of the useful solid carriers are finely ground koalinite, bentonite, talc, attapulgite, and the like. When making up a solid formulation, a more even distribution of chemical can be obtained if it is dissolved in a volatile solvent prior to mixing. After mixing, the solvent is evaporated by any convenient method. Any solvent in which the active ingredient is soluble and which may be readily removed is acceptable provided it does not leave any residue which in itself is toxic.
- Liquid compositions of the active components of the invention may be dispersions or emulsions. Since the useful compounds disclosed herein are substantially insoluble in water, it is desirable to add a small amount of an inert, non-phytotoxic organic solvent which can be readily dispersed in the aqueous medium to produce a uniform dispersion.
- An effective liquid formulation includes the active component, acetone, water, and a surface active agent such as Tween-20 (polyoxyethylene sor-bitan monolaurate).
- Atlox 6-3396 and Atlox G-2081 which are, respectively, a blend of polyoxyethylene sorbitol esters and esters of mixed fatty and resin acids and alkyl aryl sulfonates, and a blend of polyoxyethylene sorbintan esters of fatty and resin acids and alkyl aryl sulfonates.
- control can be achieved by dusting in the manner as for other materials such as DDT, or by spraying a liquid formulation just to the point of run-off it treating pest laden plants.
- control can be achieved by dusting in the manner as for other materials such as DDT, or by spraying a liquid formulation just to the point of run-off it treating pest laden plants.
- their walkways may be dusted or sprayed, or the pest may be directly contacted with a formulation containing an effective toxic amount of the active compound.
- Example 1 (a) S,S-diprpyl phosphorochloridodithioite.Six hundred and seven parts (8 moles) of propyl mercaptan was added to 550 parts (4 moles) of -PCl at 25-30 C. in 1 hour and 55 minutes, while stirring, after which the mixture was allowed to stand overnight. The product was separated by fractionally distilling at mm. of Hg up to a boiling point of 140 C.
- Example 2 Three grams of whole wheat flour was placed in a 20 x 90 petri dish. One ml. of acetone containing 8, 4, 2, 1, or 0.5 mg. of the test com-pound was poured over the flour and mixed therewith. After a two-hour waiting period to allow for evaporation of the acetone, the treated flour was pushed to one side of the petri dish. Adult confused flour beetles, Triboliumconfusum, were placed in the treated flour and the dish was covered with a cheese cloth top. Compounds at each concentration were run in triplicate, and the results below, taken after 48 hours, are averages of the replicates.
- Example 4 Pepper plants infested with aphids, Macrosiphum sp., were sprayed with a 1000 p.p.m. concentration of compound 543. The formulation was made by mixing 100 mg. of the compound with 5 drops of Tween-20, m1. of acetone and 90 ml. of water. As in the preceding example, the plants were sprayed just to the point of liquid run-off. After 48 hours, 96% of the aphids were dead.
- Example 5 Cotton plants heavily infested with aphids, Aphis gosypii, were sprayed to liquid run-off with a 100 p.p.m. concentration of compound 507 (formulated as in Example 4).
- Example 6 Adult German cockroaches, Blattella germanica (Linn), were placed in a 14 cm. x 20 cm. test jar, around the rim of which had been placed a ring of white petroleum jelly to prevent escape of the roaches.
- a Masonite panel (4.5" x 4.5") was sprayed with a 1% solution of compound 104 in acetone such that A gm. of the chemical was deposited on the panel. Means for keeping the panel from contact with the bottom of the jar were provided, and the panel was placed in the jar. After 24 hours, of the roaches were dead.
- Example 7 A 14 cm. x 20 cm. test jar was prepared as described in Example 6, and German cockroaches were placed therein. A formulation containing 0.125% of active ingredient was prepared by dis-solving mg. of compound 104 in 10 ml. of acetone, adding 5 ml. of Tween-20 thereto, and dilutingto 100 ml. with water. Formulations containing 0.062% and 0.031% of the compound were then prepared by diluting portions of the 0.125% concentrate with the appropriate amount of water.
- An emulsifiable formulation of compound 104 was prepared and mixed with sterile soil in an amount to give 2.5 p.p.m. of the compound by weight of the soil. Mixing was accomplished in a Twin Shell blender, the blender being allowed to run until the soil was evenly moistened. The treated soil was transferred to glass jars containing 10 symphylans. The results were checked by removing the soil and counting the live symphylans. Compound 104 was found to give excellent control over a long period when checking results at 4-week intervals. Thus, during a 16-week period, there was 85-10070 control of successive infestations of the pest.
- a method of controlling insects, mites, and symphylans which comprises applying thereto a toxic quantity of the compound of the formula (C H S) POCH L 2.
- a method of controlling insects, mites, and symphylans which comprises applying thereto a toxic quantity of an aqueous formulation of a compound of the formula (C3H7S)2POCH3.
- a method of controlling insects, mites, and symphylans which comprises applying thereto a toxic quantity of a mixture of the compound (C3H7S) POCH and a finely divided carrier.
- a method of controlling insects, mites, and symphylans which comprises thereto a composition comprising a minor amount of the compound (C3H7S)2POCH3.
- a method of controlling insects, mites, and symphylans which comprises applying thereto a toxic amount of a compound of the formula wherein R is selected from the group consisting of methyl and ethyl, R is a member of the group consisting of propyl and butyl when R is methyl, and R is propyl when R is ethyl.
- a method of controlling insects, mites, and symphylans which comprises applying thereto a toxic amount of a mixture of a compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,852,549 9/1958 Coover 16722 2,875,229 2/1959 Coover 167-22 2,875,230 2/1959 Coover 167-22 2,881,201 4/1959 Schrader 167-22 2,992,264 7/1961 Miller 167-22 3,112,244 11/1963 Goyette 16722 OTHER REFERENCES Armed Services Technical Information Agency-NRL Report C-3323 (1948), pages 63, 84.
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- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
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- Plant Pathology (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Description
n 32%,393 Ice Patented August 23, 1966 3,268,393 METHOD OF KILLING INSECTS WITH PHOSPHQR- ODITHIOITES AND PHOSPHORODITHIOATES John H. Wilson, Jr., Richmond, Va., assignor to Mobil Oil Corporation, a corporation of New York No Drawing. Filed May 17, 1965, Ser. No. 456,474 17 Claims. (Cl. 16722) This application is a continuation-in-part of pending application No. 147,157, filed October 24, 196-1, now abandoned.
This invention relates to the control of agricultural pests. More particularly it relates to the control of insects, mites, and symphylans with S,S-dipropyl O-methyl phosphoridithioite or a compound of the formula wherein R' is selected from the group consisting of methyl and ethyl, R is a member of the group consisting of propyl and butyl when R is methyl, and R is propyl when R is ethyl.
The compounds of this invention may be prepared by reacting substantially two moles of the appropriate alkyl rnercaptan with essentially one mole of phosphorus trichloride, and reacting the resulting dialkyl phosphorochloridithioite with one mole of methyl or ethyl alcohol. The S,S-dialkyl O-methyl or O-ethyl phosphorodithioite thus formed may be converted to the corresponding dithioate by reacting it with an oxidant such as hydrogen peroxide.
The organophosphorus compounds of the invention have been found useful for the control or insects, mites, and symphylans at concentrations of from 0.005 to 1% by weight of the total formulation. Because of the low rates required for effective control, it would be impracticable to apply the compounds as such. It is desirable, therefore, to apply them in the form of liquid sprays, or as formulations containing solid vehicles or extenders, in either case the formulation comprising a minor amount of the active ingredient. For example, the compounds may be mixed with a finely divided solid carrier as an aid in uniform distribution. As a general rule, acceptable solid carriers are those which are non-hygroscopic (to prevent caking) and inert (to eliminate undesirable adverse effects upon the formulation itself and upon the environment to be treated). Some of the useful solid carriers are finely ground koalinite, bentonite, talc, attapulgite, and the like. When making up a solid formulation, a more even distribution of chemical can be obtained if it is dissolved in a volatile solvent prior to mixing. After mixing, the solvent is evaporated by any convenient method. Any solvent in which the active ingredient is soluble and which may be readily removed is acceptable provided it does not leave any residue which in itself is toxic.
Liquid compositions of the active components of the invention may be dispersions or emulsions. Since the useful compounds disclosed herein are substantially insoluble in water, it is desirable to add a small amount of an inert, non-phytotoxic organic solvent which can be readily dispersed in the aqueous medium to produce a uniform dispersion. An effective liquid formulation includes the active component, acetone, water, and a surface active agent such as Tween-20 (polyoxyethylene sor-bitan monolaurate). Included among the other surface active agents which the art will recognize as useful are Atlox 6-3396 and Atlox G-2081, which are, respectively, a blend of polyoxyethylene sorbitol esters and esters of mixed fatty and resin acids and alkyl aryl sulfonates, and a blend of polyoxyethylene sorbintan esters of fatty and resin acids and alkyl aryl sulfonates.
When treating for insects, mites or symphylans, it is necessary to apply only enough of the material to assure contact with these pests. For example, when treating plants infested with one or more of these, control can be achieved by dusting in the manner as for other materials such as DDT, or by spraying a liquid formulation just to the point of run-off it treating pest laden plants. For killing household pests, their walkways may be dusted or sprayed, or the pest may be directly contacted with a formulation containing an effective toxic amount of the active compound.
The following examples will specifically illustrate the preparation and use of the compounds of the invention. It is to be understood that the illustrated concentrations of active ingredients are representative of effective ranges only, and they are not unnecessarily to limit the invention. Since the total range of effective concentrations has not been delimited, it is contemplated that a lesser amount than the lowest disclosed concentration will be effective. Furthermore, although it is evident that maximum control can be expected at the highest disclosed rates, under certain conditions, such as weather and resistance of the pest, a higher rate of application may be necessary for complete control. In regard to the maximum concentration, it is contemplated that the only limiting factor, aside from economics, will be the concentration at which plant injury may become a critical factor. In the examples, parts refers to parts by weight.
Example 1 (a) S,S-diprpyl phosphorochloridodithioite.Six hundred and seven parts (8 moles) of propyl mercaptan was added to 550 parts (4 moles) of -PCl at 25-30 C. in 1 hour and 55 minutes, while stirring, after which the mixture was allowed to stand overnight. The product was separated by fractionally distilling at mm. of Hg up to a boiling point of 140 C.
(b) S,S-dipr0pyl O-me'thyl phosphorodithioite.-Fiftyfour parts of the product from (a) was added at 05 C., while stirring, over a period of 30 minutes to a mixture of 12 parts of methanol and 38 parts of triethylamine in hexane. The reaction mixture was allowed to stir for an additional hour at 0-5 C. The mass was filtered to remove the amine hydrochloride. An atmosprere of N was maintained during reaction, stirring and filtration to prevent oxidation. After filtration to remove the hydrochloride, the hexane was fractionated, first at atmospheric pressure, then to 30 mm. at a final pot temperature of 100 C. The residue was distilled at mm. of Hg to yield the desired product boiling at 130-140 C.
(c) S,S-dipr0pyl O-methyl phosphorodithioate.-Fourteen parts of hydrogen peroxide was added to 21.2 parts of the product from (b) in refluxing benzene. Slight cooling was necessary because of theexothermic nature of the reaction. After the addition was completed, stirring continued for minutes. The mass was cooled and Washed with two SO-part portions of 5% sodium hydroxide. Aqueous and organic layers were separated and the solvent was removed at a pressure of 30 mm. of Hg and a temperature of C. The resulting residue was 3 distilled at 8 mm. of Hg, yielding the product fraction at 138150 C.
S,S-di butyl O-methyl phosphorodithioate and S,S-dipropyl O-ethyl phosphorodithioate were prepared in substantially the same way as described in Example 1.
The following will illustrate the eifectiveness of the compounds against insects, mites, and symphylans. For convenience, the compounds will be referred to by number as follows:
Number: Compound 543 S,S-dipropyl O-methyl phosphorodithioate. 607 S,S-dipropyl O-methyl phosphorodithioate. 104 S,S-dipropyl O-ethyl phosphorodithioate. 557 S,S-dibutyl O-methyl phosphorodithioate.
Example 2 Three grams of whole wheat flour was placed in a 20 x 90 petri dish. One ml. of acetone containing 8, 4, 2, 1, or 0.5 mg. of the test com-pound was poured over the flour and mixed therewith. After a two-hour waiting period to allow for evaporation of the acetone, the treated flour was pushed to one side of the petri dish. Adult confused flour beetles, Triboliumconfusum, were placed in the treated flour and the dish was covered with a cheese cloth top. Compounds at each concentration were run in triplicate, and the results below, taken after 48 hours, are averages of the replicates.
Black Valentine beans heavily infested with mites, Terranychus bimaculatus, were sprayed with 500 p.p.n1. (50 mg. of compound, 5 drops of Tween-20, 10 ml. of acetone and 90 ml. of water) and 1000 ppm. (100 mg. of compound, 5 drops of Tween-20, 1 ml. of acetone and 99 m1. of water) concentrations of active ingredients just to the point of liquid run-off. Following are the results at varying times after application:
Percent Dead After- Compound Gone,
p.p.m. 48 hrs. 72 hrs. days 3 weeks Example 4 Pepper plants infested with aphids, Macrosiphum sp., were sprayed with a 1000 p.p.m. concentration of compound 543. The formulation was made by mixing 100 mg. of the compound with 5 drops of Tween-20, m1. of acetone and 90 ml. of water. As in the preceding example, the plants were sprayed just to the point of liquid run-off. After 48 hours, 96% of the aphids were dead.
Example 5 Cotton plants heavily infested with aphids, Aphis gosypii, were sprayed to liquid run-off with a 100 p.p.m. concentration of compound 507 (formulated as in Example 4).
After 18 hours, 100% of the aphids were dead.
4 Example 6 Adult German cockroaches, Blattella germanica (Linn), were placed in a 14 cm. x 20 cm. test jar, around the rim of which had been placed a ring of white petroleum jelly to prevent escape of the roaches. A Masonite panel (4.5" x 4.5") was sprayed with a 1% solution of compound 104 in acetone such that A gm. of the chemical was deposited on the panel. Means for keeping the panel from contact with the bottom of the jar were provided, and the panel was placed in the jar. After 24 hours, of the roaches were dead.
Without changing the panel, all dead roaches were removed, and live ones were placed in the jar. Twentyfour hours later, results were taken, the dead roaches were removed and were replaced by live ones. This process was continued for 39 days, and results taken on the 40th day indicated that the residual chemical on the originally treated panel was continuing to give 100% control.
Example 7 A 14 cm. x 20 cm. test jar was prepared as described in Example 6, and German cockroaches were placed therein. A formulation containing 0.125% of active ingredient was prepared by dis-solving mg. of compound 104 in 10 ml. of acetone, adding 5 ml. of Tween-20 thereto, and dilutingto 100 ml. with water. Formulations containing 0.062% and 0.031% of the compound were then prepared by diluting portions of the 0.125% concentrate with the appropriate amount of water.
The roaches in the jar were sprayed with each of the prepared concentrations, taking care to contact all of them without wetting them unnecessarily. T 0 do this, about 10 ml. of each concentration was sprayed under a pressure of about 40 pounds, using a nozzle which gave a fine mist. This mist was passed rapidly over the jar four times, each pass being at right angles to the one before it. The results are summarized in the following table.
An emulsifiable formulation of compound 104 was prepared and mixed with sterile soil in an amount to give 2.5 p.p.m. of the compound by weight of the soil. Mixing was accomplished in a Twin Shell blender, the blender being allowed to run until the soil was evenly moistened. The treated soil was transferred to glass jars containing 10 symphylans. The results were checked by removing the soil and counting the live symphylans. Compound 104 was found to give excellent control over a long period when checking results at 4-week intervals. Thus, during a 16-week period, there was 85-10070 control of successive infestations of the pest.
Having described the invention, what is claimed is:
1. A method of controlling insects, mites, and symphylans which comprises applying thereto a toxic quantity of the compound of the formula (C H S) POCH L 2. A method of controlling insects, mites, and symphylans which comprises applying thereto a toxic quantity of an aqueous formulation of a compound of the formula (C3H7S)2POCH3.
3. The method according to claim 2 in which the aqueous formulation contains a surface active agent.
4. The method according to claim 2 in which the aqueous formulation has therein a solvent.
5 A method of controlling insects, mites, and symphylans which comprises applying thereto a toxic quantity of a mixture of the compound (C3H7S) POCH and a finely divided carrier.
6. A method of controlling insects, mites, and symphylans which comprises thereto a composition comprising a minor amount of the compound (C3H7S)2POCH3.
7. A method of controlling insects, mites, and symphylans which comprises applying thereto a toxic amount of a compound of the formula wherein R is selected from the group consisting of methyl and ethyl, R is a member of the group consisting of propyl and butyl when R is methyl, and R is propyl when R is ethyl.
8. The method as defined in claim 7 in which the compound is (C3H7S)2P(O)OCH3.
9. The method as defined in claim 7 in which the compound is (C H S) P(O)OCH 10. The method as defined in claim 7 in which the compound iS 0C2H5.
11. The method as defined in claim 7 in which the compound is applied to said insects, mites, and symphylans in the form of an aqueous emulsion thereof.
12. The method as defined in claim 11 in which the aqueous formulation has therein a surf-ace active agent.
13. The method as defined in claim 11 in which the aqueous formulation has therein a solvent.
14. A method of controlling insects, mites, and symphylans which comprises applying thereto a toxic amount of a mixture of a compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,852,549 9/1958 Coover 16722 2,875,229 2/1959 Coover 167-22 2,875,230 2/1959 Coover 167-22 2,881,201 4/1959 Schrader 167-22 2,992,264 7/1961 Miller 167-22 3,112,244 11/1963 Goyette 16722 OTHER REFERENCES Armed Services Technical Information Agency-NRL Report C-3323 (1948), pages 63, 84.
JULIAN S. LEVITT, Primary Examiner.
GEORGE A. MENTIS, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,268,393 August 23, 1966 John He Wilson, Jro
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 3, line 11, for "S,S-dipropyl O-methyl phosphorodithioate" read S,S-dipropyl O-methyl phosphorodithioite Signed and sealed this 22nd day of August 1967,,
(SEAL) Attest:
ERNEST W. SWIDER EDWARD J. BRENNER Atteeting Offioer Commissioner of Patents
Claims (1)
1. A METHOD OF CONTROLLING INSECTS, MITES, AND SYMPHYLANS WHICH COMPRISES APPLYING THERETO A TOXIC QUANTITY OF THE COMPOUND OF THE FORMULA (C3H7S)2POCH3.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL134634D NL134634C (en) | 1961-10-24 | ||
| US456474A US3268393A (en) | 1961-10-24 | 1965-05-17 | Method of killing insects with phosphorodithioites and phosphorodithioates |
| DE19661567129 DE1567129B1 (en) | 1961-10-24 | 1966-03-13 | S, S-di-n-propyl-O-ethyl-dithiophosphate and process for its preparation |
| FR53539A FR1478591A (en) | 1961-10-24 | 1966-03-15 | Method of destroying insects by means of phosphorodithioites |
| NL6605690A NL6605690A (en) | 1961-10-24 | 1966-04-28 | |
| GB20440/66A GB1154211A (en) | 1961-10-24 | 1966-05-09 | Method of Controlling Pests |
| JP41014726A JPS4931099B1 (en) | 1961-10-24 | 1966-05-17 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14715761A | 1961-10-24 | 1961-10-24 | |
| US456474A US3268393A (en) | 1961-10-24 | 1965-05-17 | Method of killing insects with phosphorodithioites and phosphorodithioates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3268393A true US3268393A (en) | 1966-08-23 |
Family
ID=26844644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US456474A Expired - Lifetime US3268393A (en) | 1961-10-24 | 1965-05-17 | Method of killing insects with phosphorodithioites and phosphorodithioates |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3268393A (en) |
| JP (1) | JPS4931099B1 (en) |
| DE (1) | DE1567129B1 (en) |
| GB (1) | GB1154211A (en) |
| NL (2) | NL6605690A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3705241A (en) * | 1966-12-01 | 1972-12-05 | Nihon Tokushu Noyaku Seizo Kk | Fungicidal process employing organic phosphorous acid esters |
| US3961043A (en) * | 1970-08-12 | 1976-06-01 | Mobil Oil Corporation | Deodorized pesticidal organothiophosphorus compounds |
| US4000271A (en) * | 1972-08-25 | 1976-12-28 | Mobil Oil Corporation | Deodorized organothiophosphorus compounds with reduced toxicity |
| JPS5566596A (en) * | 1978-08-08 | 1980-05-20 | Sumitomo Chem Co Ltd | Agent for controlling rice blast by applying to water surface or soil |
| US4304587A (en) * | 1979-11-05 | 1981-12-08 | Stauffer Chemical Company | Formulations for improved pesticide-fertilizer compositions |
| EP0043926A1 (en) * | 1980-07-10 | 1982-01-20 | BASF Aktiengesellschaft | 2-Thiocyanoethyl-phosphoric-acid derivatives, process for preparing them and their use as pesticides |
| US4313941A (en) * | 1978-02-09 | 1982-02-02 | Duphar International Research B.V. | Stabilized granular nematicidal and insecticidal composition having O-ethyl-S,S-dipropyl dithiophosphate as an active substance |
| EP0139466A2 (en) * | 1983-09-12 | 1985-05-02 | Sumitomo Chemical Company, Limited | A dithiolphosphoric acid ester as a soil pesticide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2852549A (en) * | 1956-02-14 | 1958-09-16 | Eastman Kodak Co | Preparation of neutral mixed phosphates by interaction of phosphates |
| US2875229A (en) * | 1956-02-14 | 1959-02-24 | Eastman Kodak Co | Preparation of neutral mixed phosphates from trialkyl phosphates and carboxylic acid esters |
| US2875230A (en) * | 1956-02-14 | 1959-02-24 | Eastman Kodak Co | Preparation of neutral mixed phosphates from trialkyl phosphates and alcohols |
| US2881201A (en) * | 1954-12-04 | 1959-04-07 | Bayer Ag | Substituted mercaptoalkyl esters of phosphoric acids and their derivatives |
| US2992264A (en) * | 1960-05-11 | 1961-07-11 | American Cyanamid Co | New synthesis of phosphorodithioate esters |
| US3112244A (en) * | 1961-04-21 | 1963-11-26 | Virginia Carolina Chem Corp | Method for controlling nematodes with phosphorothioites and phosphorothioates |
-
0
- NL NL134634D patent/NL134634C/xx active
-
1965
- 1965-05-17 US US456474A patent/US3268393A/en not_active Expired - Lifetime
-
1966
- 1966-03-13 DE DE19661567129 patent/DE1567129B1/en active Pending
- 1966-04-28 NL NL6605690A patent/NL6605690A/xx unknown
- 1966-05-09 GB GB20440/66A patent/GB1154211A/en not_active Expired
- 1966-05-17 JP JP41014726A patent/JPS4931099B1/ja active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2881201A (en) * | 1954-12-04 | 1959-04-07 | Bayer Ag | Substituted mercaptoalkyl esters of phosphoric acids and their derivatives |
| US2852549A (en) * | 1956-02-14 | 1958-09-16 | Eastman Kodak Co | Preparation of neutral mixed phosphates by interaction of phosphates |
| US2875229A (en) * | 1956-02-14 | 1959-02-24 | Eastman Kodak Co | Preparation of neutral mixed phosphates from trialkyl phosphates and carboxylic acid esters |
| US2875230A (en) * | 1956-02-14 | 1959-02-24 | Eastman Kodak Co | Preparation of neutral mixed phosphates from trialkyl phosphates and alcohols |
| US2992264A (en) * | 1960-05-11 | 1961-07-11 | American Cyanamid Co | New synthesis of phosphorodithioate esters |
| US3112244A (en) * | 1961-04-21 | 1963-11-26 | Virginia Carolina Chem Corp | Method for controlling nematodes with phosphorothioites and phosphorothioates |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3705241A (en) * | 1966-12-01 | 1972-12-05 | Nihon Tokushu Noyaku Seizo Kk | Fungicidal process employing organic phosphorous acid esters |
| US3961043A (en) * | 1970-08-12 | 1976-06-01 | Mobil Oil Corporation | Deodorized pesticidal organothiophosphorus compounds |
| US4000271A (en) * | 1972-08-25 | 1976-12-28 | Mobil Oil Corporation | Deodorized organothiophosphorus compounds with reduced toxicity |
| US4313941A (en) * | 1978-02-09 | 1982-02-02 | Duphar International Research B.V. | Stabilized granular nematicidal and insecticidal composition having O-ethyl-S,S-dipropyl dithiophosphate as an active substance |
| JPS5566596A (en) * | 1978-08-08 | 1980-05-20 | Sumitomo Chem Co Ltd | Agent for controlling rice blast by applying to water surface or soil |
| JPS5726674B2 (en) * | 1978-08-08 | 1982-06-05 | ||
| US4304587A (en) * | 1979-11-05 | 1981-12-08 | Stauffer Chemical Company | Formulations for improved pesticide-fertilizer compositions |
| EP0043926A1 (en) * | 1980-07-10 | 1982-01-20 | BASF Aktiengesellschaft | 2-Thiocyanoethyl-phosphoric-acid derivatives, process for preparing them and their use as pesticides |
| EP0139466A2 (en) * | 1983-09-12 | 1985-05-02 | Sumitomo Chemical Company, Limited | A dithiolphosphoric acid ester as a soil pesticide |
| EP0139466A3 (en) * | 1983-09-12 | 1985-09-25 | Sumitomo Chemical Company, Limited | A dithiolphosphoric acid ester as a soil pesticide |
| US4596796A (en) * | 1983-09-12 | 1986-06-24 | Sumitomo Chemical Company, Limited | Dithiolphosphoric acid ester as a soil pesticide |
Also Published As
| Publication number | Publication date |
|---|---|
| NL6605690A (en) | 1966-11-18 |
| DE1567129B1 (en) | 1972-01-13 |
| JPS4931099B1 (en) | 1974-08-19 |
| NL134634C (en) | |
| GB1154211A (en) | 1969-06-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: RHONE-POULENC, INC. BLACK HORSE LANE, MONMOUTH JUN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. AS OF JULY 31, 1981.;ASSIGNOR:MOBIL OIL CORPORATION, A NY CORP.;REEL/FRAME:003996/0522 Effective date: 19810731 |